Preparation of ethers



' yield of ether has been reduced.

Patented Nov. 4, 194"` 'v UNITED sTArEs PATENT IoFFlcE 2,430,381;y w y PREPARATION F ETHERS Paul H. Carnell, Bartlesville, Okla., assigner to Phillips Petroleum Com Delaware pany, a corporation o! A Application January 11, 1945, Serial No. 572,336 'z claims. (ci. 26o-614) of thefollowlng steps:

1. Reaction of suitable alcohols with anhy-l tendency to undergo oxidation-reduction reactions causes the formation of an objectionable proportion of undesirable, sulfur containing, by-

products. In contrast, hydrofluoric acid is free from the disadvantages of sulfuric acid.

Although anhydrous hydroiluoricl acid has been -tried in small-scale scientific experiments vfor the preparation of various simple and com plex ethers from the corresponding alcohols and/or olens, no fully satisfactory process for The invention is an advantageous combination drous hydroiluorlc acid under selected conditions. A Wide range of pressures and temperatures may be used. In the reaction between concentrated hydrofluoric acid and ethyl alcohol, the acid concentration should be 95 to 100 per cent to insure I maximum dehydration in a short contact time, thereby minimizing polymer formation. The mol ratio of acid .to alcohol may vary, but is usually about 2:1. 'I'he temperature may vary but is preferably G-250 C.

2. Fractionation to recover a substantial proportion of substantially pure anhydrous hydrofiuoric acid, followed by dilution .of the reaction mixture and fractionation to recover ether and preparing ethers in high yield and purity with the aid of hydrofluoric acid has been available hitherto. Major difficulties have been:

1. An undesirable conversion of the alcohol or olefin' to alkyl uoride, wherefore the ultimate 2. Recovery of the ether andunreacteda1- cohol free from hydrofluoric acid without neutralizing the acid or diluting the entire quantity of acid so that none of the acid is available in a concentrated form for recycling. Reconcentration of the entire quantity of dilute acid would be lextremely costly.

The present invention comprises an improvement over those heretofore'descrbed in that` the alkyl fluoride is hydrolyzed to alcohol and the alcohol is converted to ether, thus producing an increase in the ultimate yield of ether. Another improvement of this invention over the alcohol.

- The reaction mixture from the initial reaction between alcohol and hydrouoric acid is fractionated to remove overhead substantially pure anhydrous acid, which is recycled to the initial reactor. The acid remaining in the reaction mixture is'then diluted by the addition of water towbelow 40 per cent, preferably about 35 perv cent or lower. Such dilution prevents distillation of undesirable ether-hydroiluoric acid and alcohol-water-hydrofiuoric acid azeotropes, and thus theether and the alcohol are recovered on further distillation in good yield essentially free from hydrofluorie acid.

3. Conversion of the olefln', and of the alkyl i fluoride formed in the initial reaction between prior artis that a substantial proportion of the hydrofluoric acid is recovered in a concentrated form and is recycled. Also, alcohol and ether are recovered in a high yield, essentially free from hydrofluoric acid. produces a product containing a minimum of undesirable impurities, in a high yield, along with optimum hydrofluoric acid recovery.

`An object of this invention is to provide a.

process for the preparation of an ether.

Another object is to provide a process for the preparation of an ether from n alcohol.

Still another object is to provide a process for the production of an ether from an olefin.

Cther objects and advantages will be apparent from the following detailed description with Thus, this invention concentrated hydrofluoricacid and alcohol, to alcohol and then to ether.

The olefin and the alkyl fluoride are converted to the alcohol by reaction with dilute hydroiluoric acid, obtained from the initial reaction between concentrated hydrofluoric' acid and alcohol, after removal of anhydrous hydrofiuori'c acid and dilution and fractionation of the reaction mixture. The concentration of the acid used in the hydrolysis of olefln and alkyl fluoride to alcohol may vary, but isusually 35 to 40 per cent. An inorganic fluoride promoter such as boron trif'luoride, potassium tantalum fluoride, potassium fluoborate, strontium fluoride, calcium fluoride, aluminum fluoride. etc., may be.

added if desired. The hydration of oleilns using concentrated hydrofluorlc acid as a catalyst and an inorganic fluoride as a promoter is disclosed in the copending patent application of Frederick E. Frey, Serial No. 559,115, filed October 17, 1944. The mol ratio of the acid to olefin, including the olefin equivalent of any alkyl fluoride, may

` vary from 10 to l, depending on the reactivity of reference to the accompanying drawing which represents diagrammatically a specific embodiment ofthe process of this invention.

the olefin or alkyl uoride. may range from 25 to 260 C., depending on the olefin or alkyl uoride.

4. Fractionaticn of the reaction mixture from The temperature.`

. 3 the hydrolysis of allwl uoride and olefin, to recover ether and alcohol. L

In the recovery of alcohol and ether from the hydrolysis mixture of olefln and alkyl fluoride with dilute hydrofluoric acid, the acid in the mixture to be fractionated is diluted to belowl about 40 per cent, preferably about 35 per cent or lower. 'I'hus formation of HF-containing azeotropes of the alcohol or the ether is avoided, and ethers and alcohols essentially free from hvdrofluoric acid are obtained.

With reference to the drawing, alcohol and concentrated hydrouoric acid are charged through line I to a first reaction zone 2 provided with means for vigorously agitating the mixture. In the reactor 2, a portion of the alcohol is converted to the corresponding ether inI the presence of the hydrouoric acid. The eiiluent of the reaction zone comprises in addition to the ether, the corresponding alkyl fluoride, the corresponding olefin, hydrouoric acid somewhat diluted with water, and a small amount of higher boiling polymeric material.w The eiiluent is passed via line 3 to a flrst fractionation 4. The first fractionation may be accomplished in one or more fractionating columns for the separation of the reactor eiliuent into its various component parts as more fully explained hereinafter. From the first fractionation, concentrated hydrofluoric acid is recycled via line 6 to the reactor 2.

Alkyl fluoride and olefin from the fractionation are,v taken off via lines 1 and 8, respectively, and passed via lines 9 and II to a second reaction zone I2. From the flrst fractionation 4, ether, alcohol, dilute hydroiluoric acid, and polymerio material is passed through line I3 to a second fractionation I4.. The second fractionation may be accomplished in'one or more fractionating columns. Ether is Withdrawn from the second fractionation via line IG as a prod-V uct of the process. Alcohol lis withdrawn via line I1 and recycled to reactor 2. Water is supplied to the second fractionation from line I8 in an amount suflicient to dilute the hydroiluoric acid present therein to the extent required to prevent the formation of alcohol-acid-water and ether-acid azeotropes. High boiling polymerio material is withdrawn vla line I9 through which it may be conducted to a depolymerization process forming no part of the present invention, or disposed of in some other suitable manner. Dilute hydrofluoric acid from the second fractionation is passed through lines 2l and II to reactor I2.

Reactor I2 is provided with means for inti- V mate contact of reactants by vigorous agitation.

Preferably, a promoter, e. g. boron trifluorlde,

is supplied to reactor I2 from a suitable source by way of line 22. Additional olefin may be supplied from line 23 and water, from line 40. In reactor I2, olefin and alkyl fluoride are converted, in the presence of dilute hydrouoric acid, to alcohol. A small amount of ether is incidentally produced in this reactor. The effluent of the second reaction comprising alcohol, ether, alkyl fluoride, olefin, and dilute hydrofluoric acid is passed via line 24 to the third fractionation 26. The third fractionation is carried out in one or more fractionation columns. Water may be supplied to the fractionation system by way of line 21 to prevent formation of alcohol-Water-acid or ether-acid azeotropes. Olefin and alkyl fluoride are withdrawn via lines 28 and 29, respectively, and recycled to reactor I2. Alcohol from the third fractionation passes i 4 through line 8| to the first reaction in reactor 2. Ether is withdrawn through line 32 as a product of the process. Dilute hydroiluoric acid is withdrawn through line 3l from which ay portion is recycled by way of line 34 to'reactor I2 andthe balance passed by way of line 38 to an acid concentration in concentratorA 31. The acid concentration may be effected by suitable means forming no part of the present invention. From the concentrator 31, concentrated hydrouoric acid is removed via line 38 and recycledy to reactor 2. Water is removed from conceny trator 31 via line 39 and recycled to fractionation steps I4 and 2S and to reactor I2. Although the process illustrated in the drawing is generally vuseful for the preparation of various low-boiling 'ethers, it is especially advantageous for the preparation of diethyl ether.

The following data illustrate some of tlie many aspects of this invention.

Enma FoRHA'rIoN BY REAcTmG ALCOHOL WITHr CoNcnN'raAm I-IYnaorLUoRrc Acm Example 1 Grams Diethyl ether 53 alcohol 40 Polymer 6-8 Gas 8 The gas was subjected to a fractional-distillation analysis, and the following percentage composition was determined:

G Wt. percent Ethylene- 9. 79 Ethyl fluoride 88. 13 E yl ether 2, 08

Ema FORMATION Wrrn Azconox. Arm DrLU'ra HF Example 2 A Monel bomb provided with a pressure gauge was charged with 41 g. of ethyl alcohol and 260 g. of 35 per cent aqueous hydrofiuorlc acid. The bomb was placed on a suitable rocker. While the bomb was rocked continuously, the temperature was increased from 45 to 252 C. during a 50min ute period. The pressure increased from 0 p. s. i. at 45 C to 760 p. s. i. at 252 C. The bomb was rocked for an additional hour while cooling. The

following products were isolated from the reaction mixture:

Grams Ethyl alcnhnl 23 Diethyl ether 2 Gas 4 The gas .was subjected to a, fractional analysis,

and the following percentage composition was deterrnineszi:l t

Gas Wt. percent Hydrolen 0, 79 Ethylene.-. 44.49 Ethyl iiuoride -i 40.94 Ether-- Y 13. 78

ALcoHoi. FORMATION WITHOUT a Paollo'rn Examples 3 to 6 A Monel bomb was charged with a given quantity of oleiin and hydrouoric acid. The bomb was provided with a suitable pressure gauge ancL" clamped to a rocker. While the bomb was rocked continuously, the temperature was increased over a speciied range for a given contact time. The following results were obtained:

3 Amonor. Peruanos nr Tm.' Palanca. or A Paonom 1f Examples 7 to 9 A Monel bomb was charged with a given quantity oi hydrotiuoric acid and a promoter. The bomb was provided with a suitable pressure gauge m and clamped to a rocker. AWhile the bomb was a, given contact time the bomb contents were discharged through a series of cooling coils, andthe reaction mixture was fractionated to determine Example; 3 4 5 Oleiin Ethylene Propylane Batam-2 Isobutylcne Acid conc., wt. percent 35 50 '40` 10 Acid, g 91 130 104 26 Oleiin, e 13 45 48 48 Mol ratio, HF:Olciin 6 6 2 Reactiontemp., C. (approx.)- 236-258 71-75 118-122 76-79 Reaction pressur p. s. i (ap rox 900 370 280 160 Reaction time, min, (approxg 80 20 50 Polymer, g. (approx.) 0 3 1 5 Alcohol yield, wt per cent oi' theot yield (approx). 30 44 35 62 RESULTS the alcohol yield. The results can be tablulated i Eample 4 as follows:

Analysis of the product gas revealed the fo1 s Y lowingl composition: Example 'i s V9 M01 Promoter BF, KaTaFf None G88 om pement 38g; HF 'g zg'a 5% ""s Fropane 41.74 40 Etlgyleng: 16 17 17 Propylene. 20,84 18) Isopropyl iiuoride Y 37.42 lo 15 15 az s 4 Example 5 zo e 4 Analysis of the product gas revealed the iol' 45 700 722 lowing composition: 24a 244 245 4.a as a as .2s as Mol .Gas percent HYnaorLUoaxc Acm-ALconor.-WAT|:R Azzo'rnorl: Butene-2 87.49 Sec. butyl iiuoride 12. 61

Eaqamples 10 to 12 Example 6 Analysis of the product gas revealed the following composition:

Mixtures of ethyl alcohol and various concentrations of hydrofluoric acid were fractionated in a copper column. Samples were collected lin Monel bombs for analysis. Hydroiiuoric acid was Gas lr'eglt determined by alkalimetric titration. Ethyl alcope hol was determined by the specific gravity oi' the Isobuwlene solution obtained afterneutralization of the hy- Buneq III 916g droiluoric acid and distillation. Water was dentelle-2 5- 79 termined by difference. The results are shown in the following tabulation:

Example...v 10 v 1l 12 Acid conc., wt. per cent 35 60.

barge: v

Acid, v 91 104 156. water, v me 1m 104. Alcohol, e 66 60 Distillate fractions:

1 9547 alr- 95 ale conc. EF. 2 Fha H -alc.-Hg0 aom. HF-alc.-H,0 azeo. 3 11F-EIO accom.- HF-HOazeo IHF-H10 aseo. Alcohol recover, per cent:

.4s sa? alcohol 94 s2 o. as ce me-water aw n 1s 10o.

l These examples show the formation of a ternary acid-alcohol water azeot'rope boiling within the range of about 103 C. and containing api proximately 30 per cent hydrogen fluoride, 60 per cent ethyl alcohol, and 10 per cent water (by difference). The samples analyzed were not purified beyond the initial distilllation.

Ethyl alcohol is a member of al homologous series oi' alcohols which form ethers; the other members of the series form similar azeotropes with hydrofluoric acid and water, but naturally -the boiling point and the composition vary with the individual members.

Hrnnonooiuc Acro-ETHER Aznornors i Ezamples'13 to 15 aMixtures of diethyl ether, ethyl alcohol, water, and hydrouoric acid were fractionated in a copper column. Hydrouoric acid in the distillate fractionations was determined by alkalimetrictitration. The results are shown in the following tabulation:

This work showed the formation of a binary hydrofluoric acid-diethyl ether azeotrope that boiled at about 74 C. and contained about 40 per cent hydrouoric acid and 60 per cent ether (by difference). The ethyl alcohol was fractionated out in Example a 93 per cent recovery was obtained (B. P. 'Tl-'78 CI) I Example 16 Anhydrous hydroiluoric acid and ethyl alcohol in a ratio of about 2 mois of acid per mol of alcohol are charged to a first reaction zone and vigorously agitated for 50 minutes at 240 C. The

products of the reaction are fractionated in a rst fractionation. Ethylene (B. P. 104 C.) and ethyl uoride (B. P. -32 C.) are passedto a second reaction zone. Concentrated hydrofluoric acid is removed and recycled to the first reaction zone. The remainder of the eilluent is admixed with sufiicient water to prevent the formation of an ethyLalcohol-water-acid azeotrope or a diethyl ether-acid azeotrope. Diethyl ether is removed from the second fractionation as product. Ethyl alcohol from the second fractionation is recycled to the first reaction zone. Polymer is removed and passed to a depolymerization unit. Dilute hydrofluoric acid from the second fractionation is passed to the second reaction zone where it is admixed with ethylene and ethyl fluoride. Boron trifluoride is added as a promoter and the resulting mixture vigorously agitated for 10 minutes at 250 C. From the second reaction zone the eilluent comprising ethylene, ethyl fluoride, diethyl ether, ethyl alcohol, and dilute hydrouoric acid, is passed to a third fractionation.

Y '8 water-acid azeotrope or the ether-acid azeotrope. From the third fractionation, diethyl ether is removed as part of the product of the process.

Ethylene and ethyl fluoride separated from the l.

10 mainder of the dilute acid is passed to a concentrator containing potassium fluoride deposited on charcoal. The concentrator temperature is maintained at about 125 C. The hydrouoric acid is recovered as a coordination compound of potes# 15 sium fluoride. The water passes through the bed of potassium fluoride and is recycled to the fractionation steps. Concentrated hydrofluoric yacid -from the concentrator (recovered by heating the potassium fluoride containing the hydrofluoric 20 acid) is recycled to the first reaction zone.

I claim: 1. A process for the production of an ether which comprises subjecting an aliphatic mono- 1 hydric alcohol to the action of substantially anhydrous hydrofluoric acid at a temperature within the range of from about 200 C. to about 250 C.`

in a iirst reaction zone; subjecting the eiiiuent of the first reaction zone comprising unreacted alcohol, the corresponding olefin, the corresponding ether, the corresponding alkyl fluoride, water, and

hydrofluoric acid to fractionation; separating substantially anhydrous hydrouoric acid from the effluent of the first reaction zone and recycling same to said first reaction zone; separating said alkyl fluoride and said olefin from the eluent of the 'rst reaction zone; separating said ether from the eiiluent of the first reaction zone as a .product of the process; separating alcohol from the eilluent of the first reaction zone and re- 40 cycling same to the first reaction zone; separating dilute hydrofiuoric acid having a hydrogen fluoride concentration within the range of about l0 to about 50 per cent by weight from the eiiuent of the first reaction zone and passing same in admixture with said alkyl fluoride and vsaid olen to a second reaction zone at a temperature within the range of from about 25 C. to about 260 C. wherein alcohol is formed; subjecting the eilluent of second reaction zone comprising said alcohol, said olefin, said alkyl fluoride, said ether,

water, and hydrouoric acid to fractionation; separating said olefin and said alkyl fluoride from the eiliuent of the second reaction zone and recycling same to said second reaction zone; separatin'g alcohol from the eiliuent of said second reaction zone and recycling same to said rst reaction zone; separating ether from said second reaction zone as product of the process; and recycling dilute hydrofluoric acid from the eiiluent of said second conversion to'said second conversion.

2. A process for the production of an ether which comprises subjecting an aliphatic monohydric alcohol to the action' of substantially anhydrous hydrouoric acid in a rst reaction zone at a temperature within the range of about 200, C. to about 250 C. thereby effecting conversion of said alcohol to the corresponding ether with incidental production of the corresponding olefin,

The hydrofluoric acid in the eluent of the second the corresponding alkyl fluoride, and water; sepreaction zone is somewhat more concentrated than the acid charged to the reaction zone due to the hydrolysis of ethyl fluoride to ethyl alcohol. Sufficient water is present in the third fractionaarating said ether from the effluent of said iirst reaction zone as product;`V separatir, 'iid alkyl fluoride and said olefin from the eiiiuent of said first reaction zone and passing same to a second tion to prevent formation of either the alcoholreaction zone in admixture with dilute hydro- 9 lluoric acid having a hydrogen uoride concentration Within the range of about 10 to about 50 per cent by weight at a temperature within the range of about 25 C. to about 260 C. thereby eiecting simultaneous conversion ofl said olen and said alkyl fluoride to said alcohol and said ether; separating said ether from the eluent of said second reaction zone as product of the process; and separating said alcohol from the eilluent of said second reaction zone and passing same to said first reaction zone as part of the feed therefor. l

3. In a process for the preparation of an ether, the steps comprising subjecting an aliphatic monohydric alcohol to the action of substantially anhydrous hydrofluoric acid in a reaction zone at a temperature within the range of about 200 C. to about 250 C. thereby effecting the formation of the corresponding ether,vwith the incidental production of the corresponding olefin, the corresponding alkyl iluoride, and water; separating said alkyl fluoride and said olefin from the eiiiuent of said reaction zone; separating substantially anhydrous hydrofluoric acid from the eliluent of said reaction zone and recycling same to said reaction zone; admixing suflicient water with the remainder of the ellluent of said reaction zone comprising unreacted alcohol, ether, and dilute hydrouoric acid to reduce the concentration of hydrogen fluoride in said acid to a value less than aboutl 40 per cent by weight; subjecting the resulting mixture to fractionation; separating from said mixture said ether as a product of the process; separating unreacted alcohol from said mixture and recycling same to said reaction zone; and separating dilute hydrofluoric acid from said mixture. l

4. In a process for the preparation of an ether, the steps comprising subjecting an aliphatic olelin and the corresponding alkyl fluoride to the action of dilute hydruoric acid having a hydrogen uoride concentration Within the range of about 10 to about 50 per cent by weight in areaction zone at a temperature within the range of from about 25 C. to about 260 C. whereby the reactants are converted to the corresponding alcohol and the corresponding ether; withdrawing eilluent from said reaction zone, said effluent comprising said olefin, said alkyl uoride, said alcohol, said ether, and dilute hydrouoric acid; subjecting the resulting mixture to fractionation in the presence of sufllcient water to maintain the concentration of-hydrogen fluoride in said dilute acid less than about 40 per cent by weightand separating ether therefrom as a product of the process; separating said alkyl lluoride and 'said olefin from said mixture and recycling same to said reaction zone; separating said alcohol from said mixture; and separating dilute hydrofluoric acid from said mixture.

5. A process for the production oldiethyl ether which comprises subjecting ethyl alcohol to the action of substantially anhydrous hydrouoric acid ln a first reactionzone at a temperature within the range f about 200 C. to about 250 C. thereby eiecting conversion of said alcohol to said ether with the incidental formation of ethylene, ethyl iluoride and water; separating said ether from the efiluent of said first reaction zone Number as product; separating ethyliluoride and ethylene from the ellluent of said rst reaction and passing same to a second reaction zone in admixture with dilute hydrofluoric acid having a hydrogen fluoride nconcentration within the range of about 10 to about 50 per cent by weight at a temperature within the range of from about 25 C. to about 260 C. thereby effecting simultaneous conversion of ethylene and ethyl fluoride to ethyl alcohol and diethyl ether; separating ethyl al cohol from the eilluent of the second reaction zone and passing same to the rst reaction zone; and separating diethyl ether from the elliuent of said second reaction zone as product of the process.

6. A process for the production of diethyl ether which comprises subjecting ethyl alcohol tothe action of substantially anhydrous hydrolluoric acid having a hydrogen liuoride concentration within the range of to 100 per cent by weight in a rst reaction zone at a temperature within the range of from about 200 C. to about 250 C.

thereby effecting conversion of ethyl alcohol to diethyl ether with the incidental formation of ethylene and ethyl uoride; separating ethylene, Y

ethyl fluoride, and concentrated hydroiluoric acid from the eilluent of the first reaction zone; adding sufficient water to the remainder of the ellluent of rst reaction zone to reduce the concentration of the hydroiiuoric acid therein to less than about l35 per cent hydrogen fluoride by weight, separately recovering diethyl ether and ethyl alcohol from the resulting dilute hydrofluoric acid:

and passing said dilute hydroiluoric acid in admixture with said ethylene and ethyl iluoride separated from said effluent of said first reaction zone to a second reaction zone at a temperature within the range of about 25 C. toabout 250 C. thereby effecting conversion of said ethylene and ethyl fluoride to ethyl alcohol and diethyl ether; and separately recovering ethyl alcohol and diethyl ether from the ellluent of said second reaction zone.

'7. In the process for the production of an ether from the corresponding aliphatic monohydric alcohol by reaction of the alcohol with substantially anhydrous hydrofluoric acid, the improvement which comprises subjecting the eilluent of said reaction comprising said ether, Ihydrofluoric acid, and unreacted alcohol to fractional distillation in the presence of sufficient water to reduce the concentration of hydrogen uoride in said acid to a value below about 35 per cent by weight and separating said ether and said alcohol essentially free from hydrofluoric acid from the mixture undergoing distillation.

PAUL H. CARNELL.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Name Date Loder Nov. 1. 1938 OTHER REFERENCES Burwell. Jour. Am. Chem. Soc., vol. 64. pp. 1025- vMeslams,comp.aem1'.,vol. 115, p. 108011892).

Certicate of Correction Patent No. 2,430,388. November 4, 1947.

PAUL H. CARNELL It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 7, line 7, for distilllaton rend distillation; line 21, for fractionetons read fractions; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oice.

Signed and sealed this 27th day of January, A. D` 1948.

THOMAS F. MURPHY,

Assistant Oommssoner 0f Patents. 

